Fungicidal mixtures

ABSTRACT

A fungicidal mixture containing 
     a) the oxime ether carboxamide of the formula I ##STR1## and b) a phthalimide derivative selected from the group of compounds II and III ##STR2## in a synergistically active amount is described.

The present invention relates to a fungicidal mixture which contains

a) the oxime ether carboxamide of the formula I ##STR3## and b) aphthalimide derivative selected from the group of compounds II and III##STR4## in a synergistically active amount.

The invention additionally relates to processes for controlling harmfulfungi using mixtures of the compounds I and II or of the compounds I andIII and the use of the compound I, the compound II and the compound IIIfor the production of mixtures of this type.

The compound of the formula I, its preparation and its action againstharmful fungi are disclosed in the literature (EP-A 477 631).

The phthalimide derivatives II and III (U.S. Pat. Nos. 2,553,770;2,553,771; 2,553,776), their preparation and their action againstharmful fungi are likewise known.

With respect to a decrease in the application rates and an improvementof the spectrum of action of known compounds, the present invention isbased on mixtures which, with a reduced total amount of applied activecompounds, have an improved action against harmful fungi (synergisticmixtures).

Accordingly, the mixtures defined at the beginning have been found. Ithas additionally been found that on simultaneous joint or separateapplication of the compound I and the compound II or the compound III oron application of the compound I and the compound II or the compound IIIsuccessively harmful fungi can be controlled better than with theindividual compounds.

The compound of the formula I can be present in the E or the Zconfiguration with respect to the C═X double bond (with respect to thecarboxylic acid function group). Accordingly, it can be used in themixture according to the invention in each case either as the pure E orZ isomer or as an E/Z isomer mixture. The E/Z isomer mixture or the Eisomer is preferably used, the E isomer being particularly preferred.

Because of the basic character of the NH group, the compound I is ableto form salts or adducts with inorganic or organic acids or with metalions.

Examples of inorganic acids are hydrohalic acids such as hydrofluoricacid, hydrochloric acid, hydrobromic acid and hydriodic acid, sulfuricacid, phosphoric acid and nitric acid.

Suitable organic acids are, for example, formic acid, carbonic acid andalkanoic acids such as acetic acid, trifluoroacetic acid,trichloroacetic acid and propionic acid and also glycolic acid,thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid,cinnamic acid, oxalic acid, alkylsulfonic acids (sulfonic acids havingstraight-chain or branched alkyl radicals having 1 to 20 carbon atoms),arylsulfonic acids or -disulfonic acids (aromatic radicals such asphenyl and naphthyl which carry one or two sulfonic acid groups),alkylphosphonic acids (phosphonic acids containing straight-chain orbranched alkyl radicals having 1 to 20 carbon atoms), arylphosphonicacids or -diphosphonic acids (aromatic radicals such as phenyl andnaphthyl which carry one or two phosphoric acid radicals), the alkyl andaryl radicals being able to carry further substituents, eg.p-toluenesulfonic acid, salicylic acid, p-aminosalicylic acid,2-phenoxybenzoic acid, 2-acetoxybenzoic acid etc.

Suitable metal ions are in particular the ions of the elements of thesecond main group, in particular calcium and magnesium, of the third andfourth main group, in particular aluminum, tin and lead, as well as ofthe first to eighth subgroup, in particular chromium, manganese, iron,cobalt, nickel, copper, zinc and others. The metal ions of the elementsof the subgroups of the fourth period are particularly preferred. Themetals can in this case be present in the different valencies applicableto them.

Preferably, the pure active compounds I and II or III are employed inthe preparation of the mixtures, to which, if required, further activecompounds against harmful fungi or other pests such as insects,arachnids or nematodes, or alternatively herbicidal or growth-regulatingactive compounds or fertilizers, can be admixed.

The mixtures of the compounds I and II or I and III and the simultaneousjoint or separate use of the compounds I and II or I and III aredistinguished by an outstanding action against a wide spectrum ofphytopathogenic fungi, in particular from the Ascomycetes andBasidiomycetes class. In some cases they are systemically active and cantherefore also be employed as foliar and soil fungicides.

They have particular importance for the control of a multiplicity offungi on various crop plants such as cotton, vegetable plants (eg.cucumbers, beans and cucurbits), barley, grass, oats, coffee, maize,fruit plants, rice, rye, soybean, grape, wheat, decorative plants, sugarcane and a multiplicity of seeds.

In particular, they are suitable for the control of the followingphytopathogenic fungi: Erysiphe graminis (powdery mildew) on cereals,Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,Podosphaera leucotricha on apples, Puccinia species on cereals,Rhizoctonia species on cotton and lawns, Ustilago species on cereals andsugar cane, Venturia inaequalis (scab) on apples, Helminthosporiumspecies on cereals, Septoria nodorum on wheat, Botrytis cinerea (graymold) on strawberries and vines, Cercospora arachidicola on groundnuts,Pseudocercosporella herpotrichoides on wheat and barley, Pyriculariaoryzae on rice, Phytophthora infestans on potatoes and tomatoes,Plasmopara viticola on vines, Alternaria species on vegetables and fruitand also Fusarium and Verticillium species.

They are additionally applicable in the protection of materials (eg.wood preservation), for example against Paecilomyces variotii.

The compounds I and II or I and III can be applied simultaneouslyjointly or separately, or successively, the sequence in the case ofseparate application in general having no effect on the control success.

The compounds I and II or I and III are customarily applied in a weightratio of from 1:1 to 1:1000, preferably from 1:1 to 1:500, in particularfrom 1:3 to 1:300 (I:II or III).

Depending on the type of effect desired, the application rates of themixtures according to the invention are from 0.02 to 5 kg/ha, preferablyfrom 0.05 to 3.5 kg/ha, in particular from 0.1 to 3.5 kg/ha. Theapplication rates here for the compound I are from 0.005 to 0.5 kg/ha,preferably from 0.01 to 0.5 kg/ha, in particular from 0.01 to 0.3 kg/ha.The application rates for the compound II or the compound III arecorrespondingly from 0.1 to 5 kg/ha, preferably from 0.1 to 3.5 kg/ha.

In the treatment of seed, application rates of mixture of from 0.001 to50 g/kg of seed, preferably from 0.01 to 10 g/kg, in particular from0.01 to 5 g/kg, are in general used.

If harmful fungi which are pathogenic for plants are to be controlled,the separate or joint application of the compounds I and II or I and IIIor of the mixtures of the compounds I and II or I and III is carried outby spraying or dusting the seeds, the plants or the soils before orafter sowing of the plants or before or after emergence of the plants.

The fungicidal synergistic mixtures and the compounds I and II or I andIII according to the invention can be prepared, for example, in the formof directly sprayable solutions, powders and suspensions or in the formof high-percentage aqueous, oily or other suspensions, dispersions,emulsions, oil dispersions, pastes, dusting compositions, broadcastingcompositions or granules and applied by spraying, atomizing, dusting,broadcasting or watering. The application form is dependent on theintended use; it should in each case guarantee a dispersion of themixture according to the invention which is as fine and uniform aspossible.

The formulations are prepared in a manner known per se, eg. by additionof solvents and/or carriers. Inert additives such as emulsifiers ordispersants are customarily admixed to the formulations.

Suitable surface-active substances are the alkali metal, alkaline earthmetal or ammonium salts of aromatic sulfonic acids, eg. lignosulfonicacid, phenolsulfonic acid, naphthalenesulfonic acid anddibutylnaphthalenesulfonic acid, as well as of fatty acids, alkyl- andalkylarylsulfonates, alkyl-, lauryl ether and fatty alcohol sulfates,and also salts of sulfated hexa-, hepta- and octadecanols or fattyalcohol glycol ethers, condensation products of sulfonated naphthaleneand its derivatives with formaldehyde, condensation products ofnaphthalene or of naphthalenesulfonic acids with phenol andformaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctyl-,octyl- or nonylphenol, alkylphenol or tributylphenyl polyglycol ethers,alkylaryl polyether alcohols, isotridecyl alcohol, fattyalcohol-ethylene oxide condensates, ethoxylated castor oil,polyoxyethylene or polyoxypropylene alkyl ethers, lauryl alcoholpolyglycol ether acetate, sorbitan esters, lignin-sulfite waste liquorsor methylcellulose.

Powder, broadcasting and dusting compositions can be prepared by mixingor joint grinding of the compounds I and II or I and III or the mixtureof the compounds I and II or I and III with a solid carrier.

Granules (eg. coated, impregnated or homogeneous granules) arecustomarily prepared by binding the active compound or the activecompounds to a solid carrier.

Fillers or solid carriers used are, for example, mineral earths such assilica gel, silicic acids, silicates, talc, kaolin, limestone, lime,chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium andmagnesium sulfate, magnesium oxide, ground plastics, and fertilizerssuch as ammonium sulfates, ammonium phosphates, ammonium nitrates, ureasand vegetable products such as cereal flour, tree bark meal, wood mealand nutshell meal, cellulose powder or other solid carriers.

The formulations in general contain from 0.1 to 95% by weight,preferably from 0.5 to 90% by weight, of one of the compounds I and IIor I and III or the mixture of the compounds I and II or I and III. Theactive compounds are in this case employed in a purity of from 90% to100%, preferably from 95% to 100% (according to NMR spectrum or HPLC).

The compounds I and II or I and III and the mixtures or thecorresponding formulations are applied by treating the harmful fungi orthe plants, seeds, soils, surfaces, materials or spaces to be kept freefrom them with a fungicidally active amount of the mixture, or of thecompounds I and II or I and III in the case of separate application.Application can be carried out before or after attack by the harmfulfungi.

Examples of the synergistic action of the mixtures according to theinvention against harmful fungi.

It was possible to show the fungicidal action of the compounds and ofthe mixtures by the following tests:

The active compounds were prepared separately or jointly as a 20%strength emulsion in a mixture of 70% by weight of cyclohexanone, 20% byweight of Nekanil® LN (Lutensol® AP6, wetting agent having emulsifierand dispersant action based on ethoxylated alkylphenols) and 10% byweight of Emulphor® EL (Emulan® EL, emulsifier based on ethoxylatedfatty alcohols) and accordingly diluted to the desired concentrationwith water.

Assessment followed determination of the attacked leaf areas in percent.These percentage values were converted into degrees of action. Thedegrees of action of the active compound mixtures to be expected weredetermined according to the Colby formula [R. S. Colby, Weeds 15, (1967)20-22] and compared with the degrees of action observed.

Colby formula:

    E=x+y-x×y/100

E is the degree of action to be expected, expressed in % of theuntreated control, when using the mixture of the active compounds A andB in the concentrations a and b

x is the degree of action, expressed in % of the untreated control, whenusing the active compound A in the concentration a

y is the degree of action, expressed in % of the untreated control, whenusing the active compound B in the concentration b

At a degree of action of 0, the attack of the treated plants correspondsto that of the untreated control plants; at a degree of action of 100the treated plants showed no attack.

Activity against Botrytis cinerea (grey mold)

Paprika seedlings (variety: Neusiedler Ideal Elite) with 4-5 leaves weresprayed with the active compound preparation until dripping wet. Afterdrying off, the plants were sprayed with a conidia suspension of thefungus Botrytis cinerea and kept for 5 days at 22°-24° C. and at highatmospheric humidity. Assessment was carried out visually.

    ______________________________________                                                    Application rate                                                                           Degree of action [%]                                 Active compound                                                                           [ppm]        {observed/calculated}                                ______________________________________                                        --          --            0                                                   I           125          20                                                   III         125          80                                                   I + III     125 + 125    100/84                                               ______________________________________                                    

From the results of the test it emerges that the degree of actionobserved in a mixture ratio of 1:1 is higher than the degree of actionforecast by the Colby formula.

We claim:
 1. The fungicidal mixture containing a synergisticallyfungicidally effective amount of(a) the oxime ether carboxamide of theformula I ##STR5## and (b) a phthalimide selected from the groupconsisting of compounds II and III ##STR6## in a synergisticallyfungicidally effective weight ratio from 1:1 to 1:300.
 2. A fungicidalmixture as claimed in claim 1, containing said oxime ether carboxamideof formula I and said phthalimide II.
 3. A fungicidal mixture as claimedin claim 1, containing said oxime ether carboxamide of formula I andsaid phthalimide III.
 4. A fungicidal mixture containing asynergistically fungicidally effective amount ofa) the oxime ethercarboxamide of the formula I ##STR7## and b) a phthalimide selected fromthe group consisting of compounds II and III, ##STR8## wherein theweight ratio of the compound I to the compound II or the compound III isfrom 1:1 to 1:3.
 5. A process for controlling harmful fungi, comprisingtreating harmful fungi, their environment or plants, seeds, soils,surfaces, materials or spaces to be kept free of said harmful fungi,with the fungicidal mixture of claim 1 at an application rate of from0.02 to 5 kg/ha for plants, soils, surfaces, materials or spaces and atan application rate of 0.001 to 50 g/kg for seeds.
 6. A process asclaimed in claim 5, wherein said application rate is 0.05 to 3.5 kg/hafor plants, soils, surfaces, materials or spaces.
 7. A process asclaimed in claim 6, wherein said application rate is from 0.1 to 3.5kg/ha for plants, soils, surfaces, materials or spaces.
 8. A process asclaimed in claim 5, wherein said application rate is from 0.01 to 10g/kg for seeds.
 9. A process as claimed in claim 8, wherein saidapplication rate is from 0.01 to 5 g/kg for seeds.
 10. A process asclaimed in claim 5, wherein said application rate is from 0.005 to 0.5kg/ha of said compound I.
 11. A process as claimed in claim 10, whereinsaid application rate is from 0.01 to 0.5 kg/ha of said compound I. 12.A process as claimed in claim 11, wherein said application rate is from0.01 to 0.3 kg/ha of said compound I.
 13. A process as claimed in claim5, wherein said application rate is from 0.1 to 5 kg/ha for saidcompound II or said compound III.
 14. A process as claimed in claim 13,wherein said application rate is from 0.1 to 3.5 kg/ha for said compoundII or said compound III.
 15. A process as claimed in claim 5, whereinsaid fungi is a Ascomycetes or Basidiomycetes fungi.
 16. A process asclaimed in claim 5, wherein said fungi is selected from the groupconsisting of Erysiphe graminis, Erysiphe cichoracearum, Sphaerothecafuliginea, Podosphaera leucotricha, Puccinia sp., Rhizoctonia sp.,Ustilago sp., Venturia inaequalis, Helminthosporium sp., Septorianodorum, Botrytis cinerea, Cercospora arachidicola, Pseudocercosporellaherpotrichoides, Pyricularia oryzae, Phytophthora infestans, Plasmoparaviticola, Alternaria sp., Fursarium sp. and Verticillium sp.